CN102317168A - Method for treating inside surface of glass container, and glass container - Google Patents

Method for treating inside surface of glass container, and glass container Download PDF

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Publication number
CN102317168A
CN102317168A CN2011800001066A CN201180000106A CN102317168A CN 102317168 A CN102317168 A CN 102317168A CN 2011800001066 A CN2011800001066 A CN 2011800001066A CN 201180000106 A CN201180000106 A CN 201180000106A CN 102317168 A CN102317168 A CN 102317168A
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China
Prior art keywords
glass container
polysilazane
surface treatment
inside face
glass
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Granted
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CN2011800001066A
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Chinese (zh)
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CN102317168B (en
Inventor
盐泽和之
五郡靖弘
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Toyo Glass Co Ltd
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Toyo Glass Co Ltd
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Publication of CN102317168A publication Critical patent/CN102317168A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/003—General methods for coating; Devices therefor for hollow ware, e.g. containers
    • C03C17/004—Coating the inside
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Surface Treatment Of Glass (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)

Abstract

The amount of alkali that elutes from the inside surface of a glass container is reduced by preventing foaming, which occurs during sintering, of polysilazane that is applied to the inside surface of the glass container. It is possible to prevent foaming of polysilazane during sintering and to reduce the amount of alkali that elutes from the inside surface of the glass container by treating the inside surface of a glass container by means of: a step for coating the inside surface of a glass container with a polysilazane solution; a step for drying the polysilazane while rotating the glass container that has been inverted and inclined at a 50 to 70 angle; and a step for sintering the polysilazane.

Description

The internal surface treatment method of glass container and glass container
Technical field
The present invention relates generally to a kind of glass container and internal surface treatment method thereof that is suitable for accommodating medicine.
Background technology
In present glass drug container, handle through handling the dealkalize that glass is carried out with sulphur dioxide or fluorochlorohydrocarbon gas (Off ロ Application ガ ス), suppress alkali and precipitate in the content.
Make sulphur dioxide, sulfur trioxide gas or chlorine act on just to handle and be called as the frosting processing in the dealkalize of heated glass container, disclosed in the for example following patent documentation 1,2 etc.
The dealkalization method (fluorochlorohydrocarbon gas processing) that fluorochlorohydrocarbon gas is just acted at the heated glass container is disclosed in following patent documentation 3 grades.
In addition, and handle, for example be disclosed in the following patent documentation 4,5 etc. with the dealkalize of above-mentioned frosting processing and fluorochlorohydrocarbon gas processing.
In addition, in following patent documentation 6, disclose a kind of like this technology: the surface coated polysilazane at glass substrate forms silica-based film, processes the alkali passivating film.
The prior art document
Patent documentation 1: TOHKEMY 2000-72491 communique
Patent documentation 2: japanese kokai publication hei 2-153847 communique
Patent documentation 3: TOHKEMY 2005-170736 worker method
Patent documentation 4: japanese kokai publication sho 61-236635 communique
Patent documentation 5: japanese kokai publication hei 11-29148 communique
Patent documentation 6: japanese kokai publication hei 5-105486 communique
Summary of the invention
Invent problem to be solved
Aspect the glass container of using at medicine,, require to surpass present performance ground and suppress alkali separating out from glass container along with the raising of requirements for quality and the raising of analytic instrument precision.
The also usefulness of above-mentioned frosting processing and fluorochlorohydrocarbon gas processing though can significantly reduce the use amount of sulphur dioxide, is handled with independent use frosting and is compared, the identical or raising a little of dealkalize effect, so the inhibition effect that alkali is separated out is inadequate.
Problem of the present invention is: make from the alkali amount of separating out of glass container inside face with compared remarkable minimizing in the past.
For this reason, effectively, carry out sintering after the drying, form silica-based tunicle at the inside face coating polysilazane of glass container.
But, being coated with under the situation of polysilazane at inside face glass container, the membrane thickness unevenness of coating tunicle produces the thick film portion that is coated with the tunicle thickening, and the result is when heating, and this thick film portion generation foaming can not practicability.
As shown in Figure 1, in case to the inside face of glass container 1 coating polysilazane 3, then bottom periphery just becomes the heavy section 4 that adheres to thick polysilazane, and this heavy section 4 produces foaming during sintering as a result.
In addition, after being coated with polysilazane, as shown in Figure 2; In case be in handstand state, then sagging at the bottom central polysilazane, when polysilazane carries out drying under state like this; Then as shown in Figure 3, form heavy section 4 in bottom central, result's this heavy section 4 when sintering produces foaming.
The present invention also will make the polysilazane of coating the glass container inside face when sintering, not foam as problem.
Solve the means of problem
(technical scheme 1)
The present invention is a kind of internal surface treatment method of glass container, and this method has following operation: with the operation of polysilazane solution coat in the glass container inside face; While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And polysilazane carried out the double burned operation.
While making glass container be rotated, make the dry operation of polysilazane, preferably carry out at normal temperatures with 50～70 ° of bevelled handstand states.After this operation, sometimes at the be covered polysilazane of a bed thickness of the inside face of glass container oral area, at this moment, as long as wipe with cloth etc.Behind this air drying, preferably carry out high temperature drying (with about 100～180 ℃ dryings about 5～15 minutes).Through high temperature drying, drying time can be shortened.
The cmpd that will have (Si-N) key is called silazane, and polysilazane is with-(SiH 2NH)-as inorganic polymer elementary cell, that dissolve in organic solvent, the top of Fig. 4 shows an example of its molecular structure.When in air, it being carried out sintering, be considered to through-(SiH 2NH)-+2H 2O → SiO 2+ NH 3+ 2H 2Reaction and form the silicon dioxide tunicle shown in Fig. 4 bottom.
Polysilazane solution is the solution after with organic solvents such as xylene polysilazane being diluted, and its concentration suits about 0.5～7wt%.
As shown in Figure 5, while make polysilazane dry, can prevent that the polysilazane that is coated with from producing heavy section, the foaming of the polysilazane tunicle in the time of can preventing sintering through glass container is rotated with θ=50～70 a ° bevelled handstand state.
When glass container was in 50～70 ° of bevelled handstand states, the remaining polysilazane solution of internal tank just dripped from container finish.Because dripping, this continues about 15 minutes, so the time that container is remained on this state is more than 15 minutes, preferably more than 20 minutes.
In this occasion, produce the heavy section of polysilazane layers sometimes at the oral area inside face of glass container 5, this moment, wiping container finish such as available cloth made the attenuation of polysilazane layer.The operation of wiping container finish inside face is easy.
When the angle of glass container during less than 50 ℃, then as shown in Figure 6, might produce heavy section 4 at the shoulder inside face of container.When surpassing 70 °, produce heavy section at container bottom.
The both continuous constant angular velocity of the rotation of glass container is rotated, the also rotation at intermittence (for example with 5 minutes at interval each half-twists), but before surplus solution drips end, preferably make more than minimum rotation 1 circle (360 °) of glass container.
It can be any remaining glass container with 50～70 ° of rotatable devices of bevelled handstand state, does not limit especially.
(technical scheme 2)
In addition, the present invention is a kind of internal surface treatment method of glass container, and this method has following operation: the operation that water, acid solution or organic solvent wash glass container inside; With the operation of polysilazane solution coat in the glass container inside face; While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And polysilazane carried out the double burned operation.
While making glass container be rotated, make the dry operation of polysilazane, preferably carry out at normal temperatures with 50～70 ° of bevelled handstand states.After this operation, sometimes at the be covered polysilazane of a bed thickness of the inside face of glass container oral area, at this moment, as long as wipe with cloth etc.Behind this air drying, preferably carry out high temperature drying (with about 100～180 ℃ dryings about 5～15 minutes).Through high temperature drying, drying time can be shortened.
Through also handling with the washing and the polysilazane of glass container inside face, alkali is separated out the inhibition effect and is further improved.
The glass container inside face is only carried out polysilazane handle, alkali is separated out and is suppressed the effect deficiency.As this reason; Be considered to because of before the polysilazane tunicle becomes fine and closely woven tunicle; In the polysilazane tunicle when a large amount of alkali that exist in mother metal surface are diffused into tunicle formation; And the alkali that has high concentration on the mother metal surface, so diffusing capacity also increases in formed silica-based film, the result just separates out alkali.
Utilizing water etc. to carry out the occasion of washing procedure, because the alkali on mother metal surface reduces, so in the polysilazane tunicle that alkali can not be diffused into tunicle when forming, diffusing capacity is also minimizing in formed silica-based film, the result can suppress alkali and separate out.
In the occasion that water washs the glass container inside face,, for example can that kind as shown in Figure 7 carry out though do not limit washing methods especially.
In the figure, with the inside that feed pipe 2 inserts the glass container 1 of upright or handstand state, water is from the powerful ejection of its leading section.Water becomes current such shown in arrow, during discharging from container finish, inner surface of container is washed.
Supply to the amount of the daily water (preferably pure water) in the container, preferably more than 2 of container capacity times.This is to remain on the inner surface of container owing to the alkali that washing precipitate in the daily water in order to prevent.
The water that pure water is aqua distillata, ion exchange water, surpass drainage (reverse osmosis membrane filtration water) or these methods combinations are processed.
After the washing, in the glass container inside face, this operation is under the state behind the daily water all dry of inner surface of container, to carry out with the polysilazane solution coat.
Through the glass container inside face being washed, can promote near the dealkalize that glass surface is with acid solution.
As acid solution, can enumerate hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrofluoric acid, acid iodide, carbonic acid etc.
The concentration of acid solution suits about 0.5～2mol%.
The amount of washing acid solution a small amount of just can, so long as the amount that inner surface of container all contacts with acid solution gets final product.
After the acid solution washing, glass container inside is washed with pure water.The amount of the pure water of this occasion is more than 2 times of container capacity preferably.
Through glass container inside being washed, can promote near the dealkalize that glass surface is with organic solvent with polar group.
As polar group, can enumerate hydroxyl, carboxyl, ketone group etc.
Alcohols is suitable as the have hydroxyl organic solvent of (OH yl), can enumerate methyl alcohol, ethanol, propyl alcohol, phenol, glycerine, ethanediol, lauryl alcohol etc.Organic acid is suitable as the organic solvent with carboxyl, can enumerate formic acid, acetate, propionic acid, benzoic acid, tartaric acid, oxalic acid, oleic acid, stearic acid etc.As organic solvent, can enumerate acetone, butanone, methyl isobutyl ketone, cyclohexanone etc. with ketone group.
Behind organic solvent washing, glass container inside is washed with pure water.The pure water amount of this occasion is more than 2 times of container capacity preferably.
(technical scheme 3)
In addition, the present invention is the internal surface treatment method like technical scheme 1 or 2 described glass containers, and wherein, the sinter point in the said sintering circuit is 300～600 ℃, and sintering time is more than 10 minutes.
Polysilazane is being carried out in the double burned operation, preferably 300～600 ℃ of sinter points, sintering time is preferably more than 10 minutes.
When sinter point during less than 300 ℃, might be able to not form the silicon dioxide tunicle of the densification of polysilazane, when surpassing 600 ℃ when carrying out sintering, the glass container distortion is big, loses the value as product.Preferred sinter point is 400～500 ℃.
When sintering time during, might be able to not form the silicon dioxide tunicle of the densification of polysilazane less than 10 minutes.The upper limit of sintering time is restriction especially not, but expended energy.
Most preferred sintering time is 30 minutes～3 hours.
The internal surface treatment method of above glass container of the present invention; Owing to do not use aggressive fumes such as sulphur dioxide; And can suppress alkali separates out from the glass container inside face; So the problem of no inner surface treatment equipment corrosion does not have the anxiety that makes the operating environment deterioration because of the leakage of aggressive fume, needn't carry out exhaust-gas treatment yet.
(technical scheme 4)
In addition, the present invention is a kind of internal surface treatment method of glass container, and this method has following operation: under heating, make a kind of in sulphur dioxide, sulfur trioxide gas, chlorine or the fluorochlorohydrocarbon gas or act on the operation of glass container inside face more than two kinds; The operation that glass container is cooled off gradually; With the operation of polysilazane solution coat in the glass container inside face; While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And polysilazane carried out the double burned operation.
While making glass container be rotated, make the dry operation of polysilazane, preferably carry out at normal temperatures with 50～70 ° of bevelled handstand states.After this operation, sometimes at the be covered polysilazane of a bed thickness of the inside face of glass container oral area, at this moment, as long as wipe with cloth etc.Behind this air drying, preferably carry out high temperature drying (with about 100～180 ℃ dryings about 5～15 minutes).Through high temperature drying, drying time can be shortened.
(technical scheme 5)
In addition; The present invention is the internal surface treatment method like technical scheme 4 described glass containers; Wherein, A kind of in making sulphur dioxide, sulfur trioxide gas, chlorine or fluorochlorohydrocarbon gas or act on more than two kinds in the said glass container inside face operation, the mean temperature of glass container is 500～700 ℃.
(technical scheme 6)
In addition, the present invention is the internal surface treatment method like technical scheme 4 or 5 described glass containers, and wherein, the sinter point in the said sintering circuit is 300～600 ℃, and sintering time is more than 10 minutes.
Through and handle with processing such as sulphur dioxide and polysilazane, alkali is separated out and is suppressed effect and further improve.
The glass container inside face is only carried out polysilazane handle, alkali is separated out and is suppressed the effect deficiency.
In the occasion of implementing processing such as sulphur dioxide; Because the alkali on mother metal surface reduces, so in the polysilazane tunicle that alkali can not be diffused into tunicle when forming, owing to having alkali hardly on the mother metal surface; Therefore diffusing capacity also reduces in formed silica-based film, and the result can suppress alkali and separate out.
Sulphur dioxide, sulfur trioxide gas, chlorine or fluorochlorohydrocarbon gas, these gases both can directly act on glass surface, also can make the material that utilizes heat and produce these gases (for example ammonium sulphate etc.) and glass contact, made consequent gas and glass reaction.
Glass mean temperature when sulphur dioxide etc. is played a role suits at 500～700 ℃, just is difficult to produce reaction less than 500 ℃, when surpassing 700 ℃, then possibly produce harmful effects such as glass deformation, rough surface.
This operation can with in the past frosting processing, fluorochlorohydrocarbon gas processing or frosting processing and fluorochlorohydrocarbon gas processing and carry out with processing identically; For example; The also glass bottle of heat for after the firm shaping on the glass container manufacturing conveyor line can carry out at the upstream side of annealing furnace.
(technical scheme 7)
In addition, the present invention is a kind of glass container, and this glass container has been implemented like each described inner surface treatment in the said technical scheme 1～6.
The invention effect
Adopt the present invention, can prevent that the polysilazane of coating the glass container inside face from producing heavy section, the foaming of polysilazane tunicle in the time of can preventing sintering.
In addition; Through with carrying out washing treatment or utilize the processing and the combination of polysilazane tunicle of sulphur dioxide etc., from the alkali amount of separating out of glass container inside face with compared remarkable minimizing in the past, therefore; Can suppress to sneak into the alkali number in the contents such as medicine that are accommodated in the glass container, improve the quality of content.
Description of drawings
Fig. 1 is polysilazane tunicle instruction diagram glass container is upright and when making polysilazane dry.
Fig. 2 is with glass container handstand and makes the dry instruction diagram of polysilazane.
Fig. 3 stands upside down glass container and polysilazane tunicle instruction diagram when making polysilazane dry.
Fig. 4 is the instruction diagram of polysilazane and silicon dioxide tunicle.
Fig. 5 is while making glass container be rotated, make the instruction diagram of the dry operation of polysilazane with 50～70 ° of bevelled handstand states.
Fig. 6 is while the instruction diagram that makes glass container when being rotated, making polysilazane dry less than 50 ° of bevelled handstand states.
Fig. 7 be the glass container inside face washing methods one the example instruction diagram.
Fig. 8 is the instruction diagram that the alkali of embodiment 1～4 is separated out test results.
Fig. 9 is that 121 ℃ * 1 hour alkali is separated out the instruction diagram of test results.
Figure 10 is that 121 ℃ * 5 hours alkali is separated out the instruction diagram of test results.
Figure 11 is 121 ℃ * 5 hours SiO 2Separate out the instruction diagram of test results.
The specific embodiment
Embodiment 1
With following main points the glass container (bottle) of inner capacities 100ml has been carried out inner surface treatment of the present invention.
(washing) with tap water
Repeat 3 times tap water filled glass container inside, discarded (below this operation being called " rinse and wash ").
(washing) with aqua distillata
Then, with aqua distillata glass container inside is rinsed and wash 3 times.
(drying)
Then, in drying oven, make glass container be in handstand state, with 80 ℃ of dryings of temperature 30 minutes.
(coating polysilazane)
To use xylene (the system GR of Northeast chemistry society xylene) the solution 3ml that contains 1wt% polysilazane (AZ electronic material society makes polysilazane NN) of dilution to put into the glass container of room temperature, will be coated with the remaining coating fluid in the interior back of full container and discharge.
Then, make glass container on one side with 60 ° of bevelled handstand states, intermittently rotation of 90 ° of ground in per 5 minutes, on one side it is carried out 20 minutes air drying.After 15 minutes, disappear from the liquid drip of the residue coating fluid of glass container oral area.
(high temperature drying)
Then, in drying oven, make glass container be in handstand state, with 80 ℃ of high temperature dryings 30 minutes.
In addition, this drying process is not limited thereto, and the posture of container also can be upright state, and drying means also can be natural seasoning.
(sintering)
Then, be that 500 ℃, sintering time are under 3 hours the condition polysilazane to be carried out sintering at sinter point.
Sintering cools off glass container after finishing gradually.The coating tunicle is not foaming fully.
Embodiment 2
Glass container (bottle) with the identical inner capacities 100ml of following main points pair and embodiment 1 carries out inner surface treatment of the present invention.
(washing) with hot water
With 60 ℃ hot water (ion exchange water) glass container inside is rinsed and to wash 1 time.
(washing) with tap water
Then, with tap water glass container inside is rinsed and wash 3 times.
(washing) with aqua distillata
Then, with aqua distillata glass container inside is rinsed and wash 3 times.
(drying)
Then, in drying oven, make glass container be in handstand state, with 80 ℃ of dryings 30 minutes.
In addition, this drying process is not limited thereto, and the posture of container also can be upright state, and drying means also can be natural seasoning.
(polysilazane processing)
Then, identical with the foregoing description 1, carry out coating, drying, sintering and the cooling gradually of polysilazane.The coating tunicle is not foaming fully.
Embodiment 3
Glass container (bottle) with the identical inner capacities 100ml of following main points pair and embodiment 1 carries out inner surface treatment of the present invention.
(washing) with dilute hydrochloric acid solution
With the dilute hydrochloric acid solution of 1mol% glass container inside is rinsed and to wash 1 time.
(washing) with tap water
Then, with tap water glass container inside is rinsed and wash 3 times.
(washing) with aqua distillata
Then, with aqua distillata glass container inside is rinsed and wash 3 times.
(drying)
Then, in drying oven, make glass container be in handstand state, with 80 ℃ of dryings 30 minutes.
In addition, this drying process is not limited thereto, and the posture of container also can be upright state, and drying means also can be natural seasoning.
(polysilazane processing)
Then, identical with the foregoing description 1, carry out coating, drying, sintering and the cooling gradually of polysilazane.The coating tunicle is not foaming fully.
Embodiment 4
Inside face to the glass container (bottle) of the inner capacities 100ml identical with embodiment 1 does not carry out washing procedure, and carries out handling (coating of polysilazane, drying, sintering and cooling gradually) with embodiment 1～3 identical polysilazane.The coating tunicle is not foaming fully.
(separating out test)
Separating out the 2nd method (121 ℃ * 1 hour) according to the Japanese Pharmacopoeia injection with the alkali of glass container carries out.
(alkali is separated out component analysis)
Utilize the atomic absorption analysis of Na to carry out.
Fig. 1 representes that 121 ℃ * 1 hour the alkali of embodiment 1～4 separates out test results.
Only carry out with respect to not carrying out washing procedure for the embodiment 4 that polysilazane handles, the alkali amount of separating out among the embodiment 1～3 all significantly reduces.
In an embodiment, the alkali amount of separating out of embodiment 2 is minimum, and secondly order is embodiment 3, embodiment 1 and embodiment 4.
In the occasion of glass container inside being washed with the organic solvent with polar group, the alkali that the occasion of washing with dilute hydrochloric acid solution among occasion of washing with hot water among discovery and the embodiment 2 and the embodiment 3 roughly is equal to is separated out the inhibition effect.
Embodiment 5
With following main points the glass container (bottle) of inner capacities 100ml is carried out inner surface treatment of the present invention.
(sulfur dioxide treatment)
Ammonium sulphate is put into glass container inside,, utilize consequent sulphur dioxide to carry out sulfur dioxide treatment glass heats to 550 ℃.
(coating polysilazane)
Then; In temperature gradually near the glass container the cool to room temperature; Put into the solution 3ml that contains 1wt% polysilazane (the system polysilazane NN of AZ electronic material society), will be coated with the remaining coating fluid in the interior back of full container and discharge with solvent xylene (the system GR of Northeast chemistry society xylene) dilution.
Then, Yi Bian make glass container with 60 ° of bevelled handstand states, intermittently rotation of 90 ° of ground in per 5 minutes, Yi Bian it is carried out 20 minutes air drying.After 15 minutes, disappear from the liquid drip of the residue coating fluid of glass container oral area.
(high temperature drying)
Then, in drying oven, make glass container be in handstand state, with 150 ℃ of high temperature dryings 10 minutes.
In addition, drying is not limited thereto, and the posture of container also can be upright state, and drying means also can be natural seasoning.
(coating number of times)
The glass container that preparation has respectively been carried out 1 time glass container to the coating of described polysilazane and high temperature drying operation and repeated 3 times, 5 times and 7 times.
(sintering)
Then, polysilazane is carried out sintering.
Under the condition of 400 ℃ of sinter points and 500 ℃, carry out.
Sintering time is 30 minutes and 3 hours.
Sintering cools off glass container after finishing gradually.The coating tunicle is not foaming fully.
Embodiment 6
The glass container (bottle) of the inner capacities 100ml identical with embodiment 5 is not carried out sulfur dioxide treatment and carry out the inner surface treatment of embodiment 6 with following main points.
(coating polysilazane)
To use xylene (the system GR of Northeast chemistry society xylene) the solution 3ml that contains 1wt% polysilazane (AZ electronic material society makes polysilazane NN) of dilution to put into the glass container of room temperature, will be coated with the remaining coating fluid in the interior back of full container and discharge.
Then, Yi Bian make glass container with 60 ° of bevelled handstand states, intermittently rotation of 90 ° of ground in per 5 minutes, Yi Bian it is carried out 20 minutes air drying.After 15 minutes, disappear from the liquid drip of the residue coating fluid of glass container oral area.
(high temperature drying)
Then, in drying oven, make glass container be in handstand state, with 150 ℃ of dryings 10 minutes.
In addition, drying is not limited thereto, and the posture of container also can be upright state, and drying means also can be natural seasoning.
(coating number of times)
The glass container that preparation has respectively been carried out 1 time glass container to the coating of described polysilazane and drying process and repeated 3 times, 5 times and 7 times.
(sintering)
Then, polysilazane is carried out sintering.
Under the condition of 500 ℃ of sinter points, carry out.
Sintering time is 3 hours.
Sintering cools off glass container after finishing gradually.The coating tunicle is not foaming fully.
(comparative example)
Identical with embodiment 5, the glass container of ammonium sulphate being put into inner capacities 100ml is inner, with glass heats to 550 ℃, utilizes consequent sulphur dioxide to carry out sulfur dioxide treatment, handle and do not carry out polysilazane, with it as comparative example.
(separating out test)
Separating out the 2nd method (121 ℃ * 1 hour) according to the Japanese Pharmacopoeia injection with the alkali of glass container carries out.
In addition, also carried out to separate out the test of time expand to 5 hour.
(analysis)
(1) the alkali amount of separating out
Utilize atomic absorption analysis to carry out the component analysis of separating out of Na.
(2) SiO 2The amount of separating out
SiO 2The amount of separating out is used to measure from the blue colour developing of molybdic acid of the 6.2.4 operation (7) of the quantivative approach of 6. silicon dioxide of JIS R3101 " analysis of soda lime glass ".
Fig. 9 representes that 121 ℃ * 1 hour alkali of embodiment 5,6 and comparative example separates out test results.
In the figure, square dot is embodiment 5, and its each point is each aviation value of 1 of test body of 400 ℃ of sinter points and 500 ℃ (sintering time all is 3 hours).In addition, confirm almost not have difference for the test body of 400 ℃ of sinter points and 500 ℃.
The triangle form point is embodiment 6 (only polysilazane processing), and its each point is the aviation value of 2 test bodies.
Circular point is comparative example (an only sulfur dioxide treatment), is the aviation value of 2 test bodies.
Like what can know from Fig. 9; The coating number of times of embodiment 6 (only polysilazane processing) is that its alkali of glass container of 1 time is separated out and suppressed effect and obviously descend, even also be for 3 times that to be coated with 7 times also be about 5 times alkali amount of separating out of embodiment 5 for about 10 times alkali amount of separating out of embodiment 5 even be coated with.
Comparative example (only sulfur dioxide treatment) is about 7.5 times alkali amount of separating out of embodiment 5.
Embodiment 5 does not have because of the variation of the coating number of times caused alkali amount of separating out basically, the coating number of times be 1 time just enough.
So; And the embodiment 5 that has used sulfur dioxide treatment and polysilazane to handle; For embodiment 6 (only polysilazane processing) and comparative example (only sulfur dioxide treatment); Have further alkali and separate out the inhibition effect, this is from the result of sulfur dioxide treatment only and the unthinkable composite effect of polysilazane process result only.
121 ℃ * 5 hours alkali of expression embodiment 5 and comparative example is separated out test results among Figure 10.
In the figure, square dot is that sinter point is that 500 ℃, sintering time are 3 hours embodiment 5, and its each point is the aviation values of 2 test bodies.
The triangle form point is that sinter point is that 500 ℃, sintering time are 30 minutes embodiment 5, and its each point is the aviation values of 2 test bodies.
Circular point is comparative example (an only sulfur dioxide treatment), is the aviation value of 2 test bodies.
As shown in the drawing, sintering time is 30 minutes and 3 hours basic indifferences, even 30 minutes also enough.Comparative example is the alkali amount of separating out about 6 times for embodiment 5.
121 ℃ * 5 hours SiO of expression embodiment 5 and comparative example among Figure 11 2Alkali is separated out test results.
In the figure, square dot is that sinter point is that 500 ℃, sintering time are 3 hours embodiment 5, and its each point is the aviation values of 2 test bodies.
The triangle form point is that sinter point is that 500 ℃, sintering time are 30 minutes embodiment 5, and its each point is the aviation values of 2 test bodies.
Circular point is comparative example (an only sulfur dioxide treatment), is the aviation value of 2 test bodies.
As shown in the drawing, sintering time 30 minutes and 3 hours basic indifferences, even 30 minutes also enough, SiO 2Basically do not separate out.Comparative example is the SiO about 20 times for embodiment 5 2The amount of separating out.
So, the present invention is at SiO 2Separate out that to suppress the effect aspect also be excellent.
Nomenclature
1 glass container
2 feed pipes
3 polysilazanes
4 heavy sections
5 oral area inside faces

Claims (7)

1. the internal surface treatment method of a glass container, this method has following operation:
With the operation of polysilazane solution coat in the glass container inside face;
While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And
Polysilazane is carried out the double burned operation.
2. the internal surface treatment method of a glass container, this method has following operation:
The operation that water, acid solution or organic solvent wash glass container inside;
With the operation of polysilazane solution coat in the glass container inside face;
While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And
Polysilazane is carried out the double burned operation.
3. according to claim 1 or claim 2 the internal surface treatment method of glass container, wherein, the sinter point in the said sintering circuit is 300～600 ℃, sintering time is more than 10 minutes.
4. the internal surface treatment method of a glass container, this method has following operation:
Under heating, make a kind of in sulphur dioxide, sulfur trioxide gas, chlorine or the fluorochlorohydrocarbon gas or act on the operation of glass container inside face more than two kinds;
The operation that glass container is cooled off gradually;
With the operation of polysilazane solution coat in the glass container inside face;
While making glass container be rotated, make the dry operation of polysilazane with 50～70 ° of bevelled handstand states; And
Polysilazane is carried out the double burned operation.
5. the internal surface treatment method of glass container as claimed in claim 4; Wherein, A kind of in making sulphur dioxide, sulfur trioxide gas, chlorine or fluorochlorohydrocarbon gas or act on more than two kinds in the operation of said glass container inside face, the mean temperature of glass container is 500～700 ℃.
6. like the internal surface treatment method of claim 4 or 5 described glass containers, wherein, the sinter point in the said sintering circuit is 300～600 ℃, and sintering time is more than 10 minutes.
7. glass container, this glass container has been implemented like each described inner surface treatment in the said claim 1～6.
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US11208348B2 (en) 2015-09-30 2021-12-28 Corning Incorporated Halogenated polyimide siloxane chemical compositions and glass articles with halogenated polyimide siloxane low-friction coatings
CN114538790A (en) * 2021-12-31 2022-05-27 安徽登云玻璃科技有限公司 Method for treating inner surface of warm glass container and glass container
CN115003641A (en) * 2019-12-05 2022-09-02 Sgd股份有限公司 Device for treating glass containers, comprising a chamber for metering a treatment substance with a double shutter, and associated method
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US10737973B2 (en) 2012-02-28 2020-08-11 Corning Incorporated Pharmaceutical glass coating for achieving particle reduction
US11497681B2 (en) 2012-02-28 2022-11-15 Corning Incorporated Glass articles with low-friction coatings
US11939259B2 (en) 2012-02-28 2024-03-26 Corning Incorporated Pharmaceutical glass coating for achieving particle reduction
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US11737951B2 (en) 2012-02-28 2023-08-29 Corning Incorporated Glass articles with low-friction coatings
US11124328B2 (en) 2012-06-07 2021-09-21 Corning Incorporated Delamination resistant glass containers
US11608290B2 (en) 2012-06-28 2023-03-21 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10787292B2 (en) 2012-06-28 2020-09-29 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10786431B2 (en) 2012-11-30 2020-09-29 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance
US10813835B2 (en) 2012-11-30 2020-10-27 Corning Incorporated Glass containers with improved strength and improved damage tolerance
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US11951072B2 (en) 2012-11-30 2024-04-09 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US11963927B2 (en) 2012-11-30 2024-04-23 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance
US10899659B2 (en) 2014-09-05 2021-01-26 Corning Incorporated Glass articles and methods for improving the reliability of glass articles
US11208348B2 (en) 2015-09-30 2021-12-28 Corning Incorporated Halogenated polyimide siloxane chemical compositions and glass articles with halogenated polyimide siloxane low-friction coatings
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